Lakes from basic dyrstuffs



Patented July 24, I934 rant- Friedrich: Muth; lz'everkus'e manyi as n rn n) fi nt alif i'mili el W rks.

11 N w Yo k; 1C,

a corporation ofDela- No' Drawing. Application, lflonemhax; 25,-, 1932;,Serial Nm 644;3981 In Germannfimnmbcr 1.,

, scree (01. 260-18) British Patents:v 173;3 1f3,"&l1d, 211,108) with aheavy metal included in,;thehydrogen sulfide group or thaammonium;sulfide group, in the usualscheme of 'q alitative analysis, or with acompound of" one of the said metals or with 0,;- mixtures of'sa-idmetals or compounds thereof.

The p ention re a es, 1 a proce s. o preparing lakes from basicdyestufis and to the new lakes; obtained; thereby more; particularly it;relates tnlakes which, have, been prepared: by

; figmeal'ls" of aheavy metal complex compound of a non-dyeinghighmolecular sulfurized'; phenol; compound as precipitating agent.

In the art of" p zoducinglakes from basiic'dye stuns tannin'isuseditp alarge extent; as pl ecipr my itating'agent for; the said basicdyestuffs. The

lakes thus produced, however, show disadvantages-in s omerespects, Forexample, the dyestuifsatkfirst'; are completelyprecipitated upon, thesubstratum butduringthe time the precip- 15,-; itated lake isdepositing; perms the clyestnir redissolves and can no longer beprecipitatedby the addition oflfurther-- tannin. This bleedingof-"thelakacan par-tiallybe, avoided by the ad:- dition,of*tartaric-emetlc. According to' the present invention tjhese disadvantages are overcome, by using as precipitat ing: agenta heavy metalcomplexcompound; of a non-dyeing highmolecula-r; sulfurized phenclcompound;

The manufacturecf' our new lakes is in ac; cordance with theart- Offproducing lakes fromf basic dyestuffs by means of tannin, For" example,the I18W'Iak8S can be prepared by-first" producing a substratumaccording to one of- ;m the-methods known inthe art,- asis, for-example,morefully described in theexamples, adding;

thereto an aqueoussolutionof a basic dyestuff;

and-' flnally precipitating--the dyestufi upon the substratum by'add-ing an-aqueous solution of a heavy metal complexcompound of- -a nondying;

Britisn Patent 3'103458; in which complex tincompounds have beendescribed, further in Britislgfliaten 3, 13;; 365,534 and 375,885, and 5in French P te 0*,541.

These heavy metal complex compounds used in our invention are generallyobtainable by heating a' non-dyeing highmolecular sulfurized phenol (seefor example U. S. P. 1,450,463, U. S.

Reissue-Patent 17,940, reissued January 27, 1931,

andhyd oxy derivatives, withsulfur in the pres; ence of" analkali fOlf'a prplonged; time; The heavy metal complex compounds thereof are furtherobtainable byheating a phenol other than phenols containing nitrogenWithsulfuric and a caustic alkali in the presence; of a heavy metal ofthe kind referred to above or a com; poundyespecially; a: salt, thereof,or-by-heating a phenol of the kind identifiedwith sulfur; chlo; ride inthe presence of the heavy metal or metals 7 or} compounds thereof: v

'Asheavy metals the complexcompounds of sulfurized phenols ot'Whichcomeinto considerationior thasumssa-ot he int ntion, therszmav e;men ioned by was at e amnle onner, i .mmium.. ntimqm, chrom um,molagbdenum, nickel, cobalt, manganese, zinc, a1umi; nun titanium,vanadium and? tungsten, For; the purpose-ob the invention; there may beused such heavy metal complex compoundsas con; min one heavy metal i-nacomplexform, for example, chromium or tip, ell assuch com: pounds whichcontain more than one heavy metal in a complex form, for example,chromiu-m'-{-'-t-in.* It is tp be mentioned that in the manufacture of: theheavy metal complex; com; pounds -those metals; causing unfavorable sidereactions should be excluded, for: example; lead, which is known asanagent" easily combining with su f r-5, and: he efor ki a he $11 2 temhe. nsctisa vmassl r 1mm, h ch ms;- dark r-ed; ubs an es without lue:ice he j purpose in question.

The new, lakes are various' coljored' substances, insolubleinw'atenfyielding; coatings of" good loih 'fastness to light The inventionis illustrated by the following examples Without being limited thereto,the, parts being-byWeight-r Example 1.50 parts of heavy spar are made105; into a paste with parts of water. Then a solution of 10 parts ofaluminum sulfate (18% A1203) in 100 parts of water is added, and atabout 30 C. a solution of 5 parts of calcined soda in 50 parts of wateris slowly introduced, 11,0

solved in 400 parts of boiling water, and thissolution is added to thesubstratum above described. In a separate vessel a 10% aqueous solutionof 1, 4 parts of the complex tin compound of a sulfurized phenol,prepared according to Example 2 of BritishPatent 370,458, "are dissolvedin a ratio of 1: 20. This solution is slowly introduced with stirringinto the mixture of substratum and solution of dyestufi, whereby thedyestuff is precipitated.

Example 2.-In an analogous manner as described in Example 1 there isprepared -a lake consisting of the following components:

100 parts of heavy spar,

2 parts of VictoriaBlue (c ompare Colour In dex, page 186,,No. 729)',and 1 part of the complex chromium compound of a sulfurized phenol,prepared according to the process described'in British Patent 360,378;dissolved in a ratio of 1: 20.

"Example 3.In an analogous manner as described in Example 1 there isprepared a lake consisting of the following components: I

50 parts of heavy spar, 10 parts of aluminium sulfate (18% A1203)dissolved in a ratio'l: 10, 5 parts of calcined soda, dissolved in aratio 11 parts of barium chloride, dissolved in a ratio of 1: 10, 2parts of Safranine FF extra (compare Colour Index, page210, No. 841) 1:100 2 Parts of the complex molybdenum compound of a sulfurized phenol,prepared; according to the process described in British Patent 370,458,dissolved in a ratio of 1: 20.

Example 4.In an analogous manner as described in Example 1 there isprepared a lake consisting of the following components:

50 parts of heavyspar, V v

10 parts of aluminum sulfate (18% A1203), dissolved in a ratio of 1: 10

5 Parts of calcinedsoda, dissolved in a ratio 11 parts of crystallizedbarium chloride, dissolved in a ratio 1: 10

. 2 parts of Rhoduline Blue 6G (compareColour Index, page 168, No. 658)1: 100

15 parts of the complex chromium compound of a sulfurized phenoldescribed in Example 2, dissolved in a ratio of 1: 20.

Example 5.-In an analogous manner as described in Example 1 there isprepared a lake consisting of the following components:

50 parts of heavy spar 10 parts of aluminum sulfate (18% A1203),

solved in a ratio of 1: 10 i V 5 parts of calcined soda, dissolved in aratio 11 parts of barium chloride, dissolved in aratio dis- 2 parts ofSafranine FF extra (compare Colour Index, page 210, No. 841) 1: 100 2parts of a complex tin compound of a sulfurized phenol, prepared in ananalogous manner as described in Example 2 of British Patent 370,458,from 116 parts of technical cresol mixture, 43 parts of caustic soda, 60parts of sulfur, 20 parts of stannous chloride and 15 parts of chromicfluoride.

.Instead of the heavy metal complex compounds of high molecularsulfurized phenols there may be used with the same result othercompounds, for example, compounds of sulfurized phenols which contain ina complex form bismuth, antimony, copper or manganese.

We claim:

1. In the process of preparing lakes from basic dyestuffs, the stepwhich comprises precipitating the basic dyestufi bymeans of a complexcompound of a heavy metal of the group consisting of copper, tin,bismuth, cadmium, antimony, chromium, molybdenum, nickel, cobalt,manganese, zinc, aluminium, titanium, vanadium and tungsten with anon-dyeing highmolecular sulfurized phenol compound.

2. In the process of preparing lakes from basic dyestuffs, the stepwhich comprises precipitating the basic dyestuff by means of a complexcompound of a heavy metal of the group consisting of copper, tin,bismuth, cadmium, antimony, chromium, molybdenum, nickel, cobalt,manganese, zinc, aluminium, titanium, vanadium and tungsten with anon-dyeing highmolecular sulfurized phenol.

3. In the process of preparing lakes from basic dyestuffs, the stepwhich comprises precipitating the basic dyestuff by means of a complextin compound of a non-dyeing highmolecular sulfurized phenol. v

4. Addition compounds between a basic dye stuff and a complex compoundof a heavy metal of the group consisting of copper, tin, bismuth,cadmium, antimony, .chromium, molybdenum, nickel, cobalt, manganese,zinc, aluminium, titanium, vanadium and tungsten with a nondyeinghighmolecular sulfurized phenol compound.

,5. Addition compounds between a basic dyestuff and a complex compoundof a heavy metal of the group consisting of copper, tin, bismuth,

stuff and a complex chromium compound of a non-dyeinghighmolecularsulfurized phenol.

, ERICH HAR'IMANN. FRIEDRICH. MU'I'H.

